1, 3-diphenylimidazolidine and certain derivatives thereof used as acid fading inhibitors



Patented Oct. 17, 1950 1,3 -DIPHENYLIMIDAZOLIDINE AND CERTAIN DERIVATIVES THEREOF USED AS ACID FADING INHIBITORS HarryWilhelm Grimmel, Riegelsville, and Alfred Guenther, Easton, Pa., assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application October 9, 1947,

Serial No. 778,749

This invention relates to improvements in the dyeing of textile materials containing organic.

derivatives of cellulose (i. e., cellulose esters and ethers, such as cellulose acetate, ethyl cellulose, and thelike) whereby the coloratlon thereon are rendered fast to acid fading (also known as atmospheric or gas fading).

Manyof the water-insoluble dyestuffs yielding desirable shades on organic derivatives of cellulose in textile materials, and having satisfactory fastness to light, washing and other agencies, have been found to be sensitive tofading upon prolonged exposure to acid fumes, particularly the combustion products of coal, gas and other fuels, which are present in minor concentration in the atmosphere, particularly in urban communities. In some cases, the brightness of the dyeingis dulled,while in others a markedchange in the shade of the coloration occurs. This is especially true of colorations produced with santhraquinone dyes, particularly those yielding valuable blue colorations'on organic derivatives nae-sun thesecompounds:areeaposed to acid fumes, the

When textile materials dyed with colo gation changes to one of a reddish or brown.-

ish cast; ,and on continuedexposuremay change to a pink coloration. {This effect limits toa considerable extent the usefulness of such dyestuffs,

which are otherwise highly satisfactory. Sensitivity to acid fumes is not restricted to anthra quinone dyes, but is likewise noticeable in the case of dyestuffs belonging to otherclasses.

I -,-I N,umerous proposals have been made'to over-1 come .aoiclfading, ordinarily involving the fappli cation to the textile material of compounds or compositions intended to prevent such, fading of thecoloration. Such compounds or compositions are ,referred to herein as acid fadinginhibitors.

' Q'Eor commercial use, an acid fading inhibitor shduld 'bel-coljorless, adapted to withstand prolonged exposure to light and/or combustion. gases without discoloration, fast to. dry-cleaning and wetew smsg, odorlesaand non toxic in the sense that it causesno skin irritations when materials treated therewith are worn. whilemost of the acid fading inhibitorsheretofore proposed satisfy anuinber .of theserequirements, in, most cases Many, of the. proposed materials are toolsoluble 12 Claims. (01. 8--61) Water or in dry-cleaning solvents so that they are largely removed when textile materials treated therewith are subjected to customary cleansing treatments.

In addition, from the standpoint of economy and convenience, it is highly. desirable that the acid fading inhibitors be applicable to the goods to be dyed together'with the dyestuff, so that a separate pie-treatment or after-treatment can beavpided. For this purpose,the.compounds employed must have suitable solubility properties, e. g., they should be insoluble but dispersible in water, ,and should possess a natural affinity for organic derivatives of cellulose.

Moreover, since the dyeing is often carried out atelevated temperatures, it is necessary that the compounds employed have a sufiiciently high melting point to avoid fusion in the dye bath. When such fusion occurs, the molten compound forms an oil which generally separates from the dispersion and dissolves a substantial ,portionlof the dispersedwater-insoluble dyestuff. The resultingliquidoil-dye mixtureis generally deposited ,on the ugoodstobe dyed, forming unsightly spots or streaks. While many of the disclosures in-the p ior art of acid fading. inhibitors indicate that they can be applied t oltextile materials at any time during the processing thereof, including. simultaneous application with the dyestufi, many .of thesuggestedcompounds are liquid at ordinary temperatures or are solids of such low melting point thatthey are substantially useless forgxapplication from a..dyebath under the usual conditionslofcommercial dyeing.

' rWehave discovered. that. certain imidazolidine derivatives, specifically 1,3-diphenylimidazolidine and jcertainderivatives thereof, are highly effective. acid ,fadi'ngdnhibitors when applied in minor. amounts to textile materials" containing organic derivatives of cellulose colored with organic dye-.-

non solubilizing substituents as are suitable for 3 inclusion in the phenyl radicals, e. g., halogen, alkyl, nitro and cyano groups.

Thus, the acid fading inhibitors of this invention are represented by the general formula CH2CH2 X Y OH/ wherein X and Y are nuclear substituents selected from the group consisting of hydrogen and non-solubilizing groups and radicals (e. g., alkyl, halogen, nitro, and cyano groups), and R is selected from the group consisting of hydrogen, alkyl, aryl, and heterocyclic radicals which are free of solubilizing substituents. For example, as disclosed by Moos in Berichte Der Deutchen Chemischen Gesellschaft, vol. 20, page 732, 1,2,3- triphenylimidazolidine can be prepared by heating benzaldehyde with NNdiphenyl-ethylenediamine to boiling temperatures. The resulting imidazole derivative can be purified by recrystallization from alcohol, petroleum ether, benzene or other suitable solvents. 2-methyl-1,3-diphenylimidazolidine can be prepared in an analogous manner by substituting acetaldehyde for benzaldehyde in the aforesaid procedure, and Z-furyl- 1,3-ditolylimidazolidine can be similarly prepared from furfural and NN-ditolyl-ethylenediamine.

The resulting compounds have been. found eminently satisfactory as acid fading inhibitors for use in accordance with this invention They have been found to possess not only all of the desired properties required in general for acid fading inhibitors but, in addition, can be advantageously applied to textile materials con-.

taining organic derivatives of cellulose from a dye-bath together with the dyestuff. Thus, they are colorless, are notv discoloredon .prolonged exposure to light or combustion gases, are insoluble in water, and fast to dry-'cleam'ngof the textile materials with the usual dry-cleaningv solvents, so that they withstand the. effects of usual cleaning operations of materials in which they are incorporated without loss of their effectiveness. Moreover, they are odorless and nonirritating to the skin when incorporated in textile materials. In addition, they can be readily dispersed in water in the same manner as is usual for dyestuffs employed for coloring organic celluganic derivatives of cellulose.

lose derivatives, have no tendency to liquefy in water at a temperature of 45-55 C.

ing, but is most conveniently and economically carried out simultaneously with the dyeing Thus, the inhibitors of this invention can be dis-' persed in the aqueous bath by any of the methods commonly used for similar, dispersion of water-insoluble dyestuffs adapted for dyeing or For instance, they may be dissolved together with the dyestuff in a water-miscible solvent, and brought into dispersion by addition of a concentrated aqueous solution of a dispersing agent having soap-like properties and/or protective colloid action, whereupon the resulting mixture can be diluted with sufficient water to yield a dye bath of the desired concentration.

The amount of acid fading inhibitor of our invention which can be employed may be varied within rather wide limits. Thus, we have found them to be fully effective in amounts corresponding to about 1% by weight of the quantity of organic derivative of cellulose subjected to treatment therewith, and can be applied from a dyebath or treatment bath containing said compounds in concentrations from 0.01 to 0.1%, such amounts being, for example, of the order of lto 5 times the amount of dyestuif employed. These,

The following examples wherein parts and percentages are by weight illustrate the manner in which a number of acid fading inhibitors of our invention can be used. a

Example I l to 2 parts of 2-methy1-1,3-diphenylimidazolia dine and 0.6 part of a blue cellulose acetate dye consisting essentially of l-(2-hydroXy-ethylamino) 4 (monoinethylamino) anthraqui none are dissolved in a small quantity of a sol,- vent composed of equal proportions ofalcohol and acetone (or another suitable water-miscible solvent), and 40-parts of a 5% aqueous solution of N,N-oleyl-methyltaurine sodium salt, or of another suitable saponaceous dispersing agent, are added to the aforesaid solution; The resulting mixture is diluted with 5000 parts of warm One hunf dred parts of cellulose acetate silk in the form of yarn or fabric is immersed in the dye-bath, the temperature gradually raised 1 to -90 0., and

the material worked in the dye-'bathat this tem.-

perature for an hour. When the dyeing operation is complete, the cellulose acetate material is removed from the dye-bath, washed with a dilute aqueous soap solution, rinsed with water and dried. j Blue coloration of the cellulose acetate silk, dyed in the foregoing manner,shows excellent re sistance to acid fumes as demonstrated by a test wherein the dyedmaterial was exposed for a prolonged period to the combustion products of i1- luminating gas produced by1a Bunsen burner. Similar results are obtained when other cellulose acetate dyes of the anthraquinone or azo series, especially dyestuffs yielding blue comm: tion, are substituted for the blue amino-anthraquinone dyestuff of the foregoing example;-

ErampZe II 1 to 2 parts of .Z-furyle1,3-ditolylimidazolidine are dissolved, as in the preceding example, in a mixture of equal parts of alcohol. and acetone,

and 40. parts of a 5% aqueous solution of N,N-

oleyl-methyl-taurine sodium salt, or another suitable asaponaceous dispersing agent, are added. The resulting concentrated dispersion of the 1,3- ditolylimidazolidine derivative is diluted with 5000 partsof water at 45-55" C., and 100 parts of cellulose acetate :silk, previously dyed with 1,4 .di monomethylamino) anthraquinone I are worked in'the bath while gradually raising the temperature to 80 1C.,:and thereafter at the same temperature for a, period of 1% to lhour. The cellulose acetate silk 'is then removed, washed with dilute aqueous soap solution, rinsed with water anddried. Theblue coloration of the dyed material thus obtainedshows excellent.resistance to acid fading, similar to that obtained in the case of thedyed material of Example I, as

indicated by subjectin it to a similar test involving prolonged exposure to the fumes of a Bunsen burner burning illuminating gas.

Cellulosehacetateg materials dyed with other dyestufis; particularly those of the blue range, can be treated inthe same manner as in the. foregoing example, and other 1,3-diphenylimidazolidines can be employed instead of the 2-furyl- 1,3 ditolylimidazolidine of the example, with similarly advantageous rsults.

Example III .1. we parts. of 1,2,3 triphenylimidazolidine and 0.6 part of 1,4-di-(2-hydroxyethylamino)- anthraquinone (a blue cellulose acetate dyestuff) are dissolved in a small quantity of a solvent composed of equal proportions of alcohol and acetone, and parts of a 5% {aqueous solution of N,N- oleyl-methyl taurine sodium salt, or of another suitable saponaceous dispersing agent, are added to the aforesaid solution. The resulting mixture is diluted with 5000 parts of warmwater at a temperature of 110-130 F. .100 parts of cellulose cellent resistance to acid fumes when tested in the manner described in the preceding example.

Colorations on textile materialscontaining or made up of organic derivatives of cellulose other than cellulose acetate, e. g. other cellulose esters, or ethers such as ethyl cellulose, can be rendered 6 hereinbefore set forth :canz'be zused inlike manner with equally advantageous results.

If desired, the treatment of Example II can be applied to undyed textile materials containing organic derivatives of cellulose, before carrying out a dyein operation thereon in order to render the resulting coloration fast to acid fumes.

The acid fading inhibitors of this invention can be applied singly,.or combinations of two or more inhibitors can be used. i

We claim:

1.. The process for stuifs on organic derivatives .of cellulose intextile materials, which colorations are normally subject to fading when exposed to acid fumes,whicl1 comprises incorporating in such material avcolorless water insoluble 1,3-diphenylimidazolidine having the general formula CHz-CH: X

Y CH e 1 2. Theprocess for increasing the resistanceito. acid fading of colorations of water-insoluble dye,-

stuifs on organic derivatives of cellulose in textile materials, which colorations are normally subj set to fading whenexposed to acid fumes, which comprises incorporating in such material l-gm eth fast to acid fading in the same manner in the foregoing examples. Similarly, colorations produced with other dyestuffs than those of the type employed in the examples are improved to a similar degree.

Furthermore, instead of thespecific acid fading inhibitors employed in the examples, other com-- pounds corresponding to the general formula yl-,1,3-diphenylimidazolidine.

3. The process-for increasing the resistance to acid fading of colorationsof water-insoluble dye-f stuffs on organic derivatives of cellulose in textile materials, which colorations are normally subject to fading when exposed to acid fumes, which comprises incorporating in such material Z- furyll,3-ditolylimidazolidine.

4. The process for increasing the resistance to acid fading of colorations of water-insoluble dyestufison organic derivatives of cellulose in textile materials, which colorations are normally subject to fading when exposed to acid fumes, which comprises incorporating in such material 1,2,3- triphenylimidaz olidine.

5. Textile material comprising dyed fibers 'of an organic derivative of cellulose dyed with a water-insoluble .dyestuff yielding colorations on said fibers normally subject to fading when exposed to acid fumes, having incorporated in said fibers a colorless water-insoluble 1,3-diphenylimidazolidine having the general formula x onhom Y \CH/ wherein X and Y are nuclear substituents selected from the group consisting of hydrogen, alkyl,

halo, nitro and cyano groups, and R is' selected from the group consisting of hydrogen, alkyl, iaryl, and furyl radicals which are free of solubilizin substituents.

6.- Textile material comprising dyed fibers of an organic derivative of cellulose dyed with a water-insoluble dyestufi yielding colorations on said fibers normally subject to fading when exincreasing the resistance to acid fading of colorations of water-insoluble dye .posed to acid fumes, having incorporated in said fibers Z-methyl-1,3-diphenyimidazolidine.

7. Textile material comprising dyed fibers of an organic derivative of cellulose dyed With a water-insoluble dyestuif yielding colorations on said fibers normally subject to fading when exposed to acid fumes, having incorporated in said fibers Z-furyl-1,3-ditolylimidazolidine.

8. Textile material comprising dyed fibers of an organic derivative of cellulose dyed with a water-insoluble dyestuff yielding colorations on said fibers normally subject to fading when exposed to acid fumes, having incorporated in said fibers 1,2,3-triphenyimidazolidine.

9. In a process for dyein textile material containing an organic derivative of cellulose, the improvement which comprises dispersing a colorless water-insoluble 1,3-diphenylimidazolidine having the general formula wherein X and Y are nuclear substituents selected from the group consisting of hydrogen, alkyl, halo, nitro and cyano groups, and R is selected from the group consisting of hydrogen, alkyl, aryl, and furyl radicals which are free of solubilizing substituents, in a dye-bath containing a water-insoluble dyestuff for said organic derivative of cellulose, yielding colorations thereon which are normally subject to fading when ex-' posed to acid fumes, and working said material in the resulting bath until dyeing is-complete.

10. In a process for dyeing textile material containing an organic derivative of cellulose, the improvement which comprises dispersing 2-methyl- 1,3-diphenylimidazolidine in a dye-bath containing a water-insoluble dyestuff for said organic derivative of cellulose, yielding colorations thereon which are normally subject to fading when exposed to acid fumes, and working said material in the resulting bath until dyeing is complete.

11. In a process for dyeing textile material containing an organic derivative of cellulose, the improvement which comprises dispersing Z-furyll,3-dito1ylimidazolidine in a dye-bath containing:

a water-insoluble dyestulf for said organic derivative of cellulose, yielding colorations thereon.

which are normally subject to fading when ex-. posed to acid fumes, and working said material in the resulting bath until dyeing is complete.

12. In a process for dyeing textile material con HARRY WILHELM GRIMMEL.

ALFRED GUENTHERQ REFERENCES CITED The following references .are of record in the file of "this patent:

UNITED STATES PATENTS Number Name Date 2 1,930,232 Ellis' Oct. 10,1933 2,083,122 O1pin June 8, 1937 2,148,655 Seymour Feb/28,1939 2,176,506 McNally Oct. 17, 1939 2,255,690 Tinker Sept. 9,1941 2,298,401 McNally Oct. 13, 1942 2,340,375 Giles Feb. 1, 1944 

1. THE PROCESS FOR INCREASING THE RESISTANCE TO ACID FADING OF COLORATIONS OF WATER-INSOLUBLE DYESTUFFS ON ORGANIC DERIVATIVES OF CELLULOSE IN TEXTILE MATERIALS, WHICH COLORATIONS ARE NORMALLY SUBJECT TO FADING WHEN EXPOSED TO ACID FUMES, WHICH COMPRISES INCORPORATING IN SUCH MATERIAL A COLORLESS WATER INSOLUBLE 1,3-DIPHENYLIMIDAZOLIDINE HAVING THE GENERAL FORMULA 